WO2021149815A1 - Procédé de production de film de résine de polyamide - Google Patents

Procédé de production de film de résine de polyamide Download PDF

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Publication number
WO2021149815A1
WO2021149815A1 PCT/JP2021/002310 JP2021002310W WO2021149815A1 WO 2021149815 A1 WO2021149815 A1 WO 2021149815A1 JP 2021002310 W JP2021002310 W JP 2021002310W WO 2021149815 A1 WO2021149815 A1 WO 2021149815A1
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WIPO (PCT)
Prior art keywords
polyamide resin
film
resin film
monomer
mass
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PCT/JP2021/002310
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English (en)
Japanese (ja)
Inventor
彰子 黒澤
敦子 野田
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ユニチカ株式会社
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Filing date
Publication date
Application filed by ユニチカ株式会社 filed Critical ユニチカ株式会社
Priority to EP21745021.2A priority Critical patent/EP4094923A4/fr
Priority to CN202180009922.7A priority patent/CN115003735A/zh
Priority to KR1020227026856A priority patent/KR102669959B1/ko
Priority to US17/794,030 priority patent/US12012491B2/en
Priority to JP2021572825A priority patent/JP7137808B2/ja
Publication of WO2021149815A1 publication Critical patent/WO2021149815A1/fr
Priority to JP2022135448A priority patent/JP2022173206A/ja
Priority to JP2022135449A priority patent/JP2022173207A/ja
Priority to US18/308,997 priority patent/US20230257539A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/70—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for producing a polyamide resin film containing a polyamide resin using a large amount of recycled raw materials.
  • waste resin materials are used as raw material resins.
  • waste materials generated in the production of the thermoplastic resin stretched film there are, for example, wastes such as selvage trimming scraps and slit scraps, and films that have not been commercialized as defective products.
  • Material recycling is generally performed in which pellets produced by remelting these are used as a remelted resin (raw material).
  • a laminated film in which a plurality of types of resin raw materials such as a printing layer, a barrier layer, an adhesive layer, and a sealant layer are laminated, such as a packaging film, is difficult to separate into each raw material and may be difficult to recycle. ..
  • the polyamide resin suitable for the film cannot be obtained. That is, it is not possible to obtain a film having excellent strength, elongation and the like.
  • a main object of the present invention is to provide a method for producing a polyamide resin film using a polyamide resin obtained by polymerizing a recycled monomer as a recycling raw material.
  • a further object of the present invention is to provide a polyamide resin film capable of exhibiting printability equal to or higher than that of a conventional product.
  • the present invention relates to the following polyamide resin and a method for producing the same.
  • 1. It is a method of manufacturing a polyamide resin film. (1) A step of producing a monomer from the depolymerization raw material (A), (2) A step of producing a polyamide resin (B) by polymerizing using a raw material containing the monomer. (3) Step of scouring the polyamide resin (B) (4) Includes a step of stretching the unstretched film after producing an unstretched film using a starting material containing the refined polyamide resin (B). A method for producing a polyamide resin film. 2. Item 2. The production method according to Item 1, wherein the monomer contains ⁇ -caprolactam. 3. 3. Item 2.
  • Item 1 above which contains a remelted resin obtained by melting a polyamide resin (excluding the polyamide resin (B)) as a part of the starting material, and the content thereof is 1% by mass or more. The manufacturing method described in. 5.
  • Item 2. The production method according to Item 1, wherein the refined polyamide resin (B) has a relative viscosity ⁇ R of 2.5 to 4.5. 6.
  • the depolymerization raw material (A) is at least one of a polyamide 6 resin and an oligomer thereof. 7.
  • a polyamide resin film in which the number of missing dots in 1000 mm 2 medium dots of a halftone print 10% gradation portion applied to the film is 100 or less.
  • the polyamide resin film according to Item 7, wherein the content of the amino-terminal group and the carboxyl-terminal group in the polyamide resin film is 80 mmol / kg or less, respectively.
  • the ratio (minimum value / maximum value) of the minimum value to the maximum value (minimum value / maximum value) of the film impact strength under a temperature of 23 ° C.
  • Item 2 The polyamide resin film according to Item 7, which comprises a polyamide resin having a half-value width of a temperature-decreasing crystallization peak of 10 ° C. or higher. 12.
  • a polyamide resin film capable of exhibiting printability equal to or higher than that of a conventional product (new product) even when a polyamide resin obtained by polymerizing a recycled monomer is used as a recycled raw material. More specifically, in the present invention, a polyamide resin film (particularly biaxial) in which local deterioration of print appearance, deterioration of adhesion, etc. is effectively suppressed by using a polyamide resin made from a recycled monomer as a raw material. Stretched polyamide resin film) can be provided.
  • the polyamide resin film of the present invention is particularly preferably used as a packaging material because the variation in impact strength is controlled and it is excellent in general physical properties such as film elongation, wettability, and haze.
  • the resin waste material can be used as a raw material, it is possible to provide, for example, a recycled polyamide resin film having a high recycling ratio of 50% or more. As a result, the reuse of resources can be promoted, which can contribute to environmental conservation as a sustainable technology.
  • the production method of the present invention is a method for producing a polyamide resin film.
  • a step of producing a monomer from the depolymerization raw material (A) (depolymerization step) (2) A step of producing a polyamide resin (B) by polymerizing using a raw material containing the monomer (polymerization step).
  • Step of refining the polyamide resin (B) (refining step)
  • a monomer is regenerated from the depolymerization raw material (A) (hereinafter, such a monomer is referred to as a “regenerated monomer”).
  • lactams are particularly preferable, and examples thereof include ⁇ -caprolactam, enantractum, caprilactam, and lauryllactam. Of these, ⁇ -caprolactam is particularly preferable.
  • the type of the depolymerization raw material (A) is not particularly limited, and in addition to various polyamide resins, oligomers of various polyamide resins can also be used. More specifically, various resins listed in the polyamide resin (B) described later can be exemplified. Examples of the oligomer include a chain body from a dimer to a heptameric body and a cyclic body from a dimer to a quaternary body.
  • At least one of the polyamide 6 resin and its oligomer can be suitably used as the depolymerization raw material (A).
  • polyamide 6 is a resin in which ⁇ -caprolactam alone is substantially composed of ⁇ -caprolactam as a monomer unit, it is also advantageous in that it can be easily monomerized and purified and separated.
  • Polyamide resin forms include discharged resin waste including switching between brands during polymerization and switching until commercialization of film products, as well as waste such as ear trimming waste and slit waste generated during film production. Examples of defective products include films that have not been commercialized. By using these as raw materials, in addition to being able to contribute to the production of films having excellent printability and the like, it is also possible to contribute to environmental conservation by using waste materials.
  • Examples of the form of the oligomer include not only the highly water-soluble oligomer recovered from the scouring water generated during the scouring of the polyamide resin, but also the residue after filtration containing a dimer having a low water solubility. ..
  • the method for producing the monomer from the depolymerization raw material (A) is not particularly limited as long as a predetermined monomer can be obtained, but preferably the depolymerization reaction of the depolymerization raw material (A) can be adopted. That is, the raw material for depolymerization (A) can be chemically decomposed by the depolymerization reaction to preferably obtain a regenerated monomer.
  • the method and conditions of the depolymerization reaction are not particularly limited, and can be carried out according to a known method. Therefore, for example, a catalyst may or may not be used. Further, it may be in the absence of water (dry type) or in the presence of water (wet type). In particular, from the viewpoint of productivity, a method of carrying out depolymerization in hot steam in the presence of a catalyst is preferable. It is difficult to directly depolymerize a cyclic oligomer having low water solubility due to the slow hydrolysis rate of the amide bond. However, it is possible to carry out ring-opening polymerization to form a chain molecule and then depolymerize under the above conditions. A regenerated monomer can also be preferably obtained from the cyclic oligomer.
  • the polyamide resin (B) is produced by polymerizing using a raw material containing the monomer (regenerated monomer).
  • all the monomers may be a raw material composed of a regenerated monomer, but it is preferable to use a virgin monomer in combination.
  • the virgin monomer is a synonym for a regenerated monomer, and refers to a monomer that has not undergone a polymer depolymerization step.
  • Commercially available products can also be used as the virgin monomer.
  • a commercially available monomer can be used as the virgin monomer.
  • Regenerated monomers may contain by-products that are difficult to separate.
  • the crystallization rate of the polyamide resin made only of the regenerated monomer can be slightly reduced as compared with the polyamide resin made only of the virgin monomer, and the polyamide resin polymerized by using the regenerated monomer and the virgin monomer in combination can be used.
  • the crystallization rate can be further reduced.
  • the crystallization rate measures the crystallization temperature of the obtained polyamide resin (T C), the half width of the obtained crystallization peak was used as the index.
  • the half width in the present invention is usually preferably 10 ° C. or higher, more preferably 11 ° C. or higher, and most preferably 12 ° C. or higher.
  • the upper limit of the half-value width can be, for example, about 20 ° C., but is not limited thereto.
  • the content of the regenerated monomer in the raw material is not particularly limited, but from the viewpoint of widening the half width, the upper limit thereof is preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the lower limit is not particularly limited, but is preferably 5% by mass or more, and particularly preferably 10% by mass or more, from the viewpoint of increasing the recycling ratio.
  • the content of the virgin monomer in the raw material is usually preferably about 10 to 95% by mass, and more preferably 20 to 90% by mass.
  • C-CL ⁇ -caprolactam regenerated by the depolymerization reaction of the polyamide 6 resin
  • V-CL ⁇ -caprolactam
  • the polyamide resin (B) may be terminally sealed for the purpose of suppressing monomer formation at the time of melting, if necessary. Therefore, the raw material may contain an additive such as a terminal sequestering agent, if necessary.
  • the terminal sequestering agent is not particularly limited, and examples thereof include organic glycidyl ester, dicarboxylic acid anhydride, monocarboxylic acid such as benzoic acid, and diamine.
  • the polymerization method itself for obtaining the polyamide resin (B) is not particularly limited, and a known monomer polymerization method can also be adopted.
  • a method is adopted in which ⁇ -caprolactam, water and benzoic acid as a terminal sequestering agent are mixed, heated in a polymerization kettle, pressurized, and then polymerized to the desired viscosity while being depressurized and dehydrated. Can be done.
  • the polyamide resin (B) is smelted.
  • the monomer contained in the polyamide resin can be removed and the relative viscosity of the polyamide resin can be increased to a desired range, and as a result, the physical properties suitable for film formation can be obtained.
  • the refining method is not limited, but it is particularly preferable to refine the polyamide resin (B) so that the relative viscosity (25 ° C.) is within the range of about 2.5 to 4.5. Therefore, for example, it is preferable to carry out the polyamide resin (B) with hot water at 90 to 100 ° C. for about 15 to 30 hours.
  • the refining method itself, a known method such as a method of immersing the polyamide resin (B) in hot water can be adopted.
  • the polyamide resin (B) can be refined in the form of a molded product such as pellets.
  • the refining step may be performed once, but may be performed twice or more if necessary.
  • the monomers contained in the polyamide resin can be completely eluted with hot water, so that the monomer content in the polyamide resin after refining can be sufficiently reduced.
  • the polyamide resin after the refining step is preferably dried if necessary.
  • the drying conditions are not particularly limited.
  • hot air drying can be performed at about 100 to 130 ° C. for about 10 to 30 hours, but the present invention is not limited to this. More specifically, hot air drying at 110 ° C. for 20 hours can also be performed.
  • an unstretched film is prepared using a starting material containing a refined polyamide resin (B), and then the unstretched film is stretched.
  • the starting material may contain the polyamide resin (B), but may contain other components as needed.
  • a remelted resin (D) obtained by melting a polyamide resin (however, excluding the polyamide resin (B)) within a range that does not hinder the effect of the present invention. Can be made to.
  • a resin waste material of a polyamide resin particularly a polyamide 6 resin
  • examples thereof include unstretched debris, ear trimming debris, slit debris, pellets formed by remelting defective products and the like generated during the production of the polyamide resin film.
  • the content of the remelted resin (D) in the starting material is not particularly limited, but is preferably 1% by mass or more, and more preferably 5% by mass or more, from the viewpoint of increasing the recycling ratio.
  • the upper limit of the content of the remelted resin (D) is usually 75% by mass or less, particularly preferably 65% by mass or less, more preferably 50% by mass or less, and further. It is particularly preferably 40% by mass or less, and most preferably 35% by mass or less. Since the amount of molecular chain ends of the remelted resin tends to increase and the viscosity tends to decrease, and the quality stability is also inferior, when the content exceeds 75% by mass, the relative viscosity as a film raw material decreases.
  • Film scraps, defective products, etc. used as remelted resins usually contain additives such as lubricants and antioxidants, but the above content is the content including these additives.
  • the concentration of additives such as lubricants and antioxidants differs depending on the brand. Therefore, as the content of the remelted resin in the polyamide resin film increases, the haze of the obtained film, the wet tension of the film surface, printability, adhesion, etc. become more local due to the variation in the concentration distribution of the additive. May decrease.
  • the content of the remelted resin in the surface layer is preferably 50% by mass or less, and more preferably 40% by mass or less. Of these, it is most preferably 35% by mass or less.
  • the content of the remelted resin in the intermediate layer is preferably 75% by mass or less.
  • the lower limit of the content of the remelted resin in each layer can be set to, for example, about 5% by mass, but is not limited to this.
  • a polyamide resin (C) obtained by polymerizing from a raw material consisting only of a virgin monomer without containing a regenerated monomer may be contained.
  • the relative viscosity of each polyamide resin contained in the starting material is not limited, but is particularly preferably 2.5 to 4.5, and more preferably 2.8 to 4.0. ..
  • a polyamide resin having a relative viscosity of less than 2.5 is used, film formation and stretching become difficult, and even if a polyamide resin film is obtained, the mechanical properties may be significantly deteriorated. Further, when a polyamide resin exceeding 4.5 is used, the film forming property of the film may be hindered.
  • the relative viscosity in the present invention is a value measured by using a Ubbelohde viscometer in a sample solution (liquid temperature 25 ° C.) in which a resin to be measured in 96% sulfuric acid is dissolved at a concentration of 1.0 g / dl. ..
  • various starting materials such as antioxidants, ultraviolet absorbers, preservatives, antistatic agents, antiblocking agents, inorganic fine particles, etc. are included in the starting material as long as they do not adversely affect the performance of the film.
  • One or more additives can be added.
  • a lubricant may be blended in the starting material for the purpose of improving the slipperiness of the obtained film.
  • the lubricant either an inorganic lubricant or an organic lubricant can be used.
  • the lubricant include clay, talc, calcium carbonate, zinc carbonate, wallastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, magnesium aluminosilicate, glass balloon, carbon black, and the like.
  • examples thereof include zinc oxide, antimony trioxide, zeolite, hydrotalcite, layered silicate, ethylene bisstearic acid amide and the like.
  • silica is particularly preferable.
  • the content of the lubricant is not particularly limited, but the range of 0.01 to 0.3% by mass in the starting material is suitable.
  • the method for producing the unstretched film is not limited, and it can be formed by a known film forming method.
  • it can be obtained by extruding the melt of the raw material from a T-die and then cooling it with a casting roll. In this case, it is necessary to accurately control the actual temperature of the casting roll surface from the viewpoint of making the crystallinity of the unstretched film uniform.
  • the moisture content of the unstretched film it is preferable to adjust the moisture content of the unstretched film to about 2 to 10% by mass (particularly 4 to 8% by mass) as a moisture adjusting step, and then stretch the film, if necessary.
  • the water content is lower than 2% by mass, the stretching stress increases and troubles such as film cutting are likely to occur.
  • the water content is higher than 10% by mass, the thickness unevenness of the unstretched film becomes large, and the thickness unevenness of the obtained stretched film also becomes large.
  • the moisture adjusting step usually, when the moisture content of the film is low (particularly when it is less than 2% by mass), the film is placed in a moisture adjusting tank having a temperature of 40 to 90 ° C, more preferably 50 to 80 ° C.
  • the moisture content of the film is adjusted by passing it through and adjusting the passing time.
  • Pure water is usually used for the moisture adjusting tank, but if necessary, a dye, a surfactant, a plasticizer, or the like may be contained in the treatment liquid. Further, the water content may be adjusted by spraying water vapor.
  • the moisture content of the film may be adjusted by passing the film through a drying oven and adjusting the passing time.
  • the stretching method is not particularly limited, and any stretching method can be adopted.
  • the biaxial stretching method is not limited, and examples thereof include a simultaneous biaxial stretching method and a sequential biaxial stretching method.
  • the simultaneous biaxial stretching method is preferable from the viewpoint of surface balance that reduces the difference between the MD and TD directions in terms of physical properties such as tensile elongation, elastic modulus, and tensile strength.
  • the axial stretching method is preferable. These stretching methods can be appropriately selected depending on the desired film physical characteristics, applications and the like.
  • the draw ratio can be appropriately set according to, for example, the application, desired physical properties, etc., and can be, for example, 2 to 4 times in the MD direction and 2 to 4 times in the TD direction, but is not limited thereto.
  • the stretching temperature is also not limited, and can be carried out in the range of, for example, 40 to 220 ° C.
  • the stretching in the MD direction is 40 to 80 ° C.
  • the stretching in the TD direction is 80 to 150 ° C.
  • the temperature is preferably 160 to 220 ° C.
  • the obtained biaxially stretched film is preferably heat-treated for a short time at a temperature of about 150 to 220 ° C., if necessary, in order to improve dimensional stability and suppress the hot water shrinkage rate.
  • the polyamide resin film of the present invention may be subjected to surface treatment such as corona discharge treatment and easy adhesion treatment as long as the effects of the present invention are not impaired.
  • surface treatment such as corona discharge treatment and easy adhesion treatment
  • an easy-adhesion layer, a barrier coat layer, a printing layer and the like can be appropriately provided as needed.
  • the polyamide resin film of the present invention thus obtained can also be provided as a laminated body laminated with another layer, if necessary.
  • a film composed of a plurality of layers may be formed by simultaneous melt extrusion, lamination or the like at the manufacturing stage of the polyamide resin film.
  • it contains a two-kind two-layer structure in which a polyamide resin film containing a polyamide 6 resin obtained by polymerizing a regenerated monomer and a polyamide 6 resin film containing a remelted resin are laminated, and a polyamide 6 resin obtained by polymerizing a regenerated monomer.
  • a two-kind, three-layer structure in which a polyamide 6 resin film containing a remelted resin is sandwiched between the polyamide resin films may be used.
  • a polyamide 6 resin film having a layer structure that sandwiches an intermediate layer, such as a two-kind three-layer structure can increase the remelted resin content of the intermediate layer.
  • Polyamide resin film The present invention includes a polyamide resin film characterized in that the number of missing dots in 1000 mm 2 in the halftone printing 10% gradation portion applied to the film is 100 or less.
  • composition of Polyamide Resin Film The composition of the polyamide resin is not particularly limited, and examples thereof include a polyamide 6 resin using lactams such as ⁇ -caprolactam as a monomer. Further, as the other polyamide resin, for example, a polyamide resin obtained by polycondensation of lactam, ⁇ -amino acids, dibasic acids, diamines and the like having three or more membered rings can be mentioned.
  • lactams include ⁇ -caprolactam, enantractam, caprilactam, and lauryllactam, as described above.
  • ⁇ -amino acids examples include 6-aminocaproic acid, 7-aminoheptanic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and the like.
  • Dibasic acids include, for example, adipic acid, glutaric acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecadioic acid, hexadecadioic acid, eikosandionic acid, eikosadiendioic acid, 2,2. , 4-trimethyladipic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, xylylenedicarboxylic acid and the like.
  • diamines examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, pentamethylenediamine, undecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, cyclohexanediamine. , Bis- (4,4'-aminocyclohexyl) methane, metaxylylenediamine, nonanediamine, decanediamine and the like.
  • the polyamide 6 resin is preferable in the present invention because it has an excellent balance between heat resistance and mechanical properties. That is, as the polyamide resin film of the present invention, a polyamide 6 resin film is preferable.
  • the polyamide resin film of the present invention has a printability of 100 or less dots missing in 1000 mm 2 of a 10% gradation portion of halftone printing applied to the film.
  • a film having such characteristics is advantageous in printing in terms of high reproducibility in the printed appearance, particularly in the light and shade areas.
  • the number is particularly preferably 80 or less, more preferably 70 or less, and most preferably 60 or less. If the number exceeds 100, although it is a low gradation part, unevenness can be visually confirmed by gazing at it, individual differences in the design can be felt, and it may be determined that printing is defective.
  • the lower limit of the number is most preferably 0, but for example, about 30 may be used, but the number is not limited to this.
  • the polyamide resin film of the present invention preferably has a relative viscosity ⁇ R of 2.5 to 4.5, more preferably in the range of 2.8 to 4.0.
  • the relative viscosity in the present invention is a value measured by using a Ubbelohde viscometer in a sample solution (liquid temperature 25 ° C.) in which a film to be measured in 96% sulfuric acid is dissolved at a concentration of 1.0 g / dl. ..
  • a polyamide resin film having a relative viscosity of less than 2.5 may significantly deteriorate its mechanical properties or may deteriorate the evaluation of the bag-dropping test of the laminated film described later. Further, when the polyamide resin film exceeds 4.5, the uniformity of the film thickness tends to be insufficient, and the mechanical properties may be uneven.
  • the thickness accuracy of the polyamide resin film of the present invention is preferably within plus or minus 15% with respect to the target thickness, and more preferably within plus or minus 10%.
  • the extraction amount of caprolactam monomer is preferably 1.6% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.5% by mass or less. It is preferable, and most preferably 0.1% by mass or less.
  • the amount of caprolactam monomer extracted from the film exceeds 1.6% by mass, the wettability of the surface of the polyamide resin film tends to vary.
  • the adhesion between the polyamide resin film and another resin layer or ink may be locally reduced, which may reduce the number of times until bag breakage in practical performance, for example, in a bag drop test. be.
  • the polyamide resin film of the present invention preferably contains amino-terminal groups and carboxyl-terminal groups of 80 mmol / kg or less, and most preferably 70 mmol / kg or less.
  • the contents of the amino-terminal group and the carboxyl-terminal group each exceed 80 mmol / kg, the crystallization rate of the film becomes high, and the degree of local crystallization tends to vary.
  • the tensile elongation tends to decrease, the physical properties such as impact strength tend to vary, and the film may partially decrease.
  • the polyamide resin film of the present invention has a ratio (minimum value / maximum value) of 0.5 to 1.0 of the minimum value and the maximum value of the film impact strength under a temperature of 23 ° C. and a humidity of 50% RH atmosphere. It is preferable, particularly preferably 0.6 to 1.0, and most preferably 0.7 to 1.0. If the ratio is less than 0.5, it is considered that the impact resistance of the film is partially reduced, which is not practically preferable.
  • the polyamide resin film of the present invention preferably has a tensile elongation of 60% or more in the MD and TD directions, and more preferably 70% or more.
  • the polyamide resin film of the present invention preferably has a haze value of 10.0% or less, more preferably 7.0% or less, and most preferably 6.0% or less.
  • the polyamide resin film of the present invention is preferably a film obtained by the above-mentioned "1.
  • Method for producing a polyamide resin film That is, it is preferable that there is a film produced by using a raw material containing a regenerated monomer. Therefore, the polyamide resin film of the present invention is preferably a stretched film (particularly a biaxially stretched film). Thereby, each physical property as described above can be obtained more reliably.
  • the polyamide resin film of the present invention may be a polyamide resin film obtained by polymerizing a regenerated monomer alone, a mixture of two or more kinds, or a polyamide resin film containing a remelted resin described later. Further, it may be composed of a single layer, or may be a film composed of a plurality of layers formed by simultaneous melt extrusion or lamination. For example, a two-kind two-layer structure in which a polyamide resin film containing a polyamide resin in which a regenerated monomer is polymerized and a polyamide resin film containing a remelted resin are laminated, and a polyamide resin film containing a polyamide resin in which a regenerated monomer is polymerized.
  • any of two types and three layers may be used, such as sandwiching a polyamide resin film containing a remelted resin.
  • the polyamide resin film of the present invention (particularly the biaxially stretched polyamide resin film) obtained as described above has excellent tensile elongation, tensile strength, elasticity, etc. as a polyamide resin film. In addition to its mechanical properties, it also has excellent transparency, color tone, wettability, printability, etc., so it can be particularly suitably used as a packaging material.
  • the polyamide resin film of the present invention can be used alone or in the form of a laminated body by laminating with other layers.
  • an easy-adhesion layer, a barrier coat layer, a printing layer, an adhesive layer and the like can be appropriately provided as needed.
  • the polyamide resin film of the present invention is packaged by laminating it with a sealant layer such as polyolefin to form a laminated film by using a known method such as a dry laminating method or an extrusion laminating method, and heat-sealing the opposing sealant layers.
  • a sealant layer such as polyolefin
  • It can also be used as a bag (bag body).
  • bag body for example, any form such as a two-sided bag, a three-sided bag, a gassho bag, a gusset bag, a side seal bag, a stand bag, and a stand chuck bag can be adopted.
  • the packaged material is not limited, and can be widely used as a packaging material for foods and drinks, pharmaceuticals, cosmetics, chemicals, miscellaneous goods, etc.
  • the present invention also includes a laminated film including the polyamide resin film of the present invention and a sealant resin layer laminated on the polyamide resin film.
  • a laminated film can also be suitably used as a packaging material or a packaging body.
  • the polyamide resin film of the present invention has a uniform surface condition, is less likely to cause local additives, monomers, etc. to precipitate, and does not cause a local decrease in adhesion. Therefore, the resulting package is a bag-resistant bag. Excellent in sex. For example, when a package filled with water is torn due to dropping, in addition to being torn from a portion having low strength, the package may be torn from a portion having low local adhesion.
  • the laminated film of the present invention has an advantage that it is less likely to break the bag than a ready-made product.
  • the laminated film of the present invention preferably has 50 or more drops to break the bag, preferably 60 or more. Is more preferable, and 70 times or more is further preferable.
  • the bag drop test was carried out by dropping a package (heat-sealed with a width of 10 mm using two 200 mm ⁇ 300 mm laminates) filled with 1000 ml of water and 10 ml of air from a height of 1.2 m. do.
  • Raw materials B2-B4 A resin scrap (resin waste material) containing film scraps or defective products generated during the production of the polyamide 6 resin film and oligomers and the like generated during the polymerization of the polyamide 6 resin was used as the depolymerization raw material (A). Phosphoric acid is added to the depolymerization raw material (A), the depolymerization reaction is carried out under heating by a wet method, and after purification by activated carbon treatment, concentration and distillation, the regenerated ⁇ -caprolactam "C-CL" is recovered. did. On the other hand, "V-CL" is a virgin monomer, ⁇ -caprolactam.
  • C-CL and V-CL are blended so as to have the ratio (mass ratio) shown in Table 1, water and benzoic acid as an end-sealing agent are mixed, and heated, pressurized, depressurized in a polymerization kettle. After dehydration, a polymerization reaction was carried out until the desired viscosity was obtained. The required polymerization time with respect to the final target viscosity depends on the ratio of CL species. Each polymerization time is as shown in Table 1. After pelletizing the obtained polymer (resin), refining by hot water treatment at 95 ° C. was performed twice for a total of 10 hours and 15 hours, and then dried at 110 ° C. for 20 hours. In this way, a polyamide resin having a relative viscosity of 3.1 (raw materials B2 to 4) was obtained.
  • Table 1 After pelletizing the obtained polymer (resin), refining by hot water treatment at 95 ° C. was performed twice for a total of 10 hours and 15 hours, and then dried at 110 ° C
  • Raw materials B1, B5 Using C-CL, water, and benzoic acid as a terminal sequestering agent as raw materials, they were polymerized in the same manner as above, pelletized, and refined by hot water treatment at 95 ° C. for a total of 2 times, 10 hours and 15 hours. After that, it was dried at 110 ° C. for 20 hours. In this way, a polyamide resin (B1) having a relative viscosity of 3.0 was obtained. Further, it was polymerized under the same conditions as the polyamide resin (B1), pelletized, refined by hot water treatment at 95 ° C. for 18 hours, and then dried at 110 ° C. for 20 hours. In this way, a polyamide resin having a relative viscosity of 2.7 (raw material B5) was obtained.
  • Raw material B6 After polymerizing under the same conditions as the raw material B1 and pelletizing, it was refined by hot water treatment at 95 ° C. for 10 hours and then dried at 110 ° C. for 20 hours. In this way, a polyamide resin having a relative viscosity of 2.4 (raw material B6) was obtained.
  • Raw material C Using V-CL, water, and benzoic acid as a terminal sequestering agent as raw materials, they are polymerized in the same step, pelletized, and refined by hot water treatment at 95 ° C. for a total of 2 times, 10 hours and 10 hours. , 110 ° C. for 20 hours. In this way, a polyamide resin (raw material C) having a relative viscosity of 3.1 was obtained.
  • Raw material D The film scraps generated during the production of the polyamide 6 resin film were crushed and then remelted at 250 to 290 ° C. to be pelletized. Then it was dried. In this way, a remelted resin (raw material D) was obtained. The relative viscosity of the remelted resin was 2.9.
  • Silica Master E (Silica-containing polyamide resin, containing 6% by mass of silica)
  • PCM-30 manufactured by Ikegai Seisakusho
  • A1030BRF polyamide 6 resin manufactured by Unitica
  • silica 1 manufactured by Fuji Silysia Chemical Ltd., Cyricia 310P, average particle size 1.4 ⁇ m
  • Example 1 As the composition of the polyamide resin film, 97.5% by mass of a polyamide resin (raw material B1) obtained by polymerizing only C-CL and 2.5% by mass of silica master are mixed, melt-kneaded in an extruder, and supplied to a T-die. The film was discharged into a sheet, wound around a metal drum whose temperature was adjusted to 20 ° C., cooled, and then wound to obtain an unstretched film having a thickness of about 150 ⁇ m. Next, after immersing the obtained unstretched film in a moisture adjusting tank adjusted to 50 ° C. for 1 minute, the end portion was held by a clip of a tenter type simultaneous biaxial stretching device, and the MD direction was obtained under the condition of 180 ° C.
  • a polyamide resin raw material B1 obtained by polymerizing only C-CL and 2.5% by mass of silica master
  • Example 2 A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that 97.5% by mass of the polyamide resin (raw material B5) shown in Table 1 was used as the composition of the polyamide resin film. The total reproduction ratio in this film was 97.5% by mass.
  • Example 3 The composition of the polyamide resin film was the same as in Example 1 except that 97.5% of the polyamide resin (raw material B4) or (raw material B3) or (raw material B2) in Table 1 was used as shown in Table 2.
  • a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained.
  • the total reproduction ratio in this film was 87.8% by mass, 39.0% by mass, and 19.5% by mass, respectively.
  • Examples 4, 11, 18 As the composition of the polyamide resin film, the polyamide resin (raw material B1) in Table 1 and the polyamide resin (raw material C) were blended so as to have the ratio shown in Table 2, except that 97.5% of this resin was used. A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1.
  • Examples 6, 7, 9, 10, 16, 17 As the composition of the polyamide resin film, the polyamide resin (raw material B1), the polyamide resin (raw material C) in Table 1 and the remelted resin (raw material D) are blended so as to have the ratio shown in Table 2, and this resin is blended in 97.
  • a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that 5.5% by mass was used.
  • Example 8 As the composition of the polyamide resin film, the polyamide resin (raw material B3) in Table 1 and the remelted resin (raw material D) were blended so as to have the ratio shown in Table 2, except that 97.5% by mass of this resin was used. Obtained a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m in the same manner as in Example 1.
  • Examples 14, 15 As the composition of the polyamide resin film, the polyamide resin (raw material B2) in Table 1 and the remelted resin (raw material D) were blended so as to have the ratio shown in Table 2, except that 97.5% by mass of this resin was used. Obtained a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m in the same manner as in Example 1.
  • Example 12 As the composition of the polyamide resin film, the polyamide resin (raw material B1) in Table 1 and the polyamide resin (raw material C) are blended in the ratios shown in Table 2, and this resin is 97.5% by mass and the silica master is 2.5% by mass. % Mix to obtain an unstretched film in the same manner as in Example 1. Next, the unstretched film was stretched 2.8 times in the MD direction with a temperature control roll at 55 ° C., held by a clip, and stretched in the TD direction at a stretching ratio of 3.7 times under the condition of 185 ° C. ( Sequential biaxial stretching). Then, the relaxation rate in the TD direction was set to 5%, heat treatment was performed at 201 ° C.
  • the mixture was slowly cooled to room temperature, and one side was subjected to corona discharge treatment. After that, the film was wound to obtain a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m.
  • the total reproduction ratio in this film was 19.5% by mass.
  • the water content of the unstretched film was 0.5% by mass.
  • Example 19 As a polyamide resin film, a two-kind three-layer film having a thickness of 1: 1: 1 was formed. As an intermediate layer, a resin in which the polyamide resin (raw material C) in Table 1 was mixed at a ratio of 25% by mass and the remelted resin (raw material D) was mixed at a ratio of 75% by mass was arranged. The polyamide resin (B3) shown in Table 1 was arranged as both outer layers. An unstretched film was obtained in the same manner as in Example 1 except that the silica master was mixed in each layer in an amount of 2.5% by mass and co-extruded, and a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained by simultaneous biaxial stretching. rice field. The total regeneration ratio in this film was 50.4% by mass.
  • Comparative Example 1 A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that 97.5% by mass of the polyamide resin (B6) shown in Table 1 was used as the composition of the polyamide resin film.
  • Comparative Example 2 A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that 97.5% by mass of the remelted resin (D) was used as the composition of the polyamide resin film.
  • Comparative Example 3 A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 12 except that 97.5% by mass of the remelted resin (D) was used as the composition of the polyamide resin film.
  • Comparative Examples 4 and 5 As the composition of the polyamide resin film, the polyamide resin (C) and the remelted resin (D) were blended so as to have the ratios shown in Table 2, and 97.5% by mass of this resin was used. Similarly, a biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained.
  • Comparative Example 6 A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except that 97.5% by mass of the polyamide resin (C) was used as the composition of the polyamide resin film.
  • Comparative Example 7 As the composition of the polyamide resin film, 97.5% by mass of the polyamide resin (C) and 2.5% by mass of the master chip (E) are mixed, melt-kneaded in an extruder, supplied to a T-die, and discharged into a sheet. Then, the film was wound around a metal drum whose temperature was adjusted to 20 ° C., cooled, and then wound to obtain an unstretched film having a thickness of about 150 ⁇ m. At this time, the actual temperature of the metal drum, which had been temperature-controlled at 20 ° C., was observed to vary, and the crystallinity of the unstretched film also varied. A biaxially stretched polyamide resin film having a thickness of 15 ⁇ m was obtained in the same manner as in Example 1 except for this. It was confirmed that the obtained film thickness accuracy exceeded plus or minus 15%.
  • Test Example 1 The following physical characteristics were examined for the raw material polyamide resins (raw materials B1 to D) and the films obtained in each Example and Comparative Example. The results are shown in Table 3. In each measurement, a sample left in an environment of temperature 23 ° C. ⁇ humidity 50% RH for 2 hours or more was used, and measurement was performed in an atmosphere of temperature 23 ° C. ⁇ humidity 50% RH.
  • [Create calibration curve] 0.1 g of caprolactam was dissolved in 100 ml of ultrapure water to prepare a 1000 ppm solution, which was further diluted to prepare standard solutions of 100, 50, 20, 10, 5, and 2 ppm, respectively, and a calibration curve was prepared.
  • the peak top temperature at the time of temperature decrease is Tc (° C)
  • the baseline is drawn from the high temperature side. The interval between them was set to the half width (° C).
  • This gradation change version has 175 lines (175 halftone dots (dots) in a width of 1 inch) and is helio-engraved in the order of gradation 10%, 20%, 30%, 40%, 100% in the MD direction. It is a thing.
  • the depth of each gradation is 2.5 ⁇ m, 5.0 ⁇ m, 7.5 ⁇ m, 10.0 ⁇ m, and 32.0 ⁇ m, respectively, the print length of each gradation in the MD direction is 60 mm, and the print width in the TD direction is 0. It was set to 8 m.
  • Rio Alpha R39 Indigo contains 10% by mass of pigment, 15% by mass of synthetic resin, 2.5% by mass of silica, 30% by mass of ethyl acetate, 15% by mass of isopropyl alcohol, 10% by mass of propyl acetate, and 10% by mass of propylene glycol monomethyl ether.
  • the main composition is 5% by mass of n-propyl alcohol.
  • the main composition of the diluent NKFS102 is 50% by mass of ethyl acetate, 35% by mass of propyl acetate, 10% by mass of isopropyl alcohol, and 5% by mass of n-propyl alcohol.
  • the MD direction is the remaining 20 mm portion excluding the upper and lower ends 20 mm
  • the TD direction is 30 mm intervals starting from the position 100 mm from the edge of the film and starting from the 50 mm portion.
  • a total of 10 locations were evaluated. That is, as shown in FIG. 1, 10 points of the measurement areas a to j of 20 mm ⁇ 50 mm were evaluated.
  • the number of missing dots may be 100 or less in practice, but 80 or less is particularly preferable, 70 or less is more preferable, and 60 or less is most preferable.
  • ⁇ No problem was found in the halftone dot shape, and the ratio of the minimum and maximum halftone dot diameters was 0.85 or more and less than 0.9. ⁇ : Some distortion is observed in the halftone dot shape, and the ratio between the minimum and maximum halftone dot diameters is 0.75 or more and less than 0.85. X ... The halftone dot shape is distorted, the size is uneven, and the ratio between the minimum and maximum halftone dot diameters is less than 0.75.
  • the corona-treated surface of the film was measured using 36.0 to 54.0 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).
  • Wetting tensions were measured at five measurement points at intervals of 200 mm from the center to both ends in the TD direction. This was measured every 1 m in the MD direction, and a total of 50 points were measured.
  • Table 3 shows the minimum and maximum values of the wet tension measurement values at 50 locations.
  • the wetting tension is usually 44 mN / m or more practical, but it is particularly preferable that it is 46 mN / m or more.
  • the sealing condition was 160 ° C. ⁇ 1 second.
  • the prepared three-sided bag is filled with 1000 ml of water, the air in the bag is released, the other side is heat-sealed with a width of 10 mm, 10 ml of air is sealed using a syringe, and the test sample sealed by heat-sealing again is used. Made.
  • the sealing condition was 160 ° C. ⁇ 1 second.
  • Test A in which the test sample is dropped in this way, and then Test B, in which one short side of the test sample is dropped so as to hit the SUS plate, are alternately performed until the test sample is sacked, until the sack is broken. The number of drops of test A or B was measured.
  • test sample has two film surfaces and two short sides
  • same film surface or the same short side was dropped so as to hit the SUS plate.
  • the biaxially stretched polyamide resin films of Examples 1 to 19 are polyamide resin films using a polyamide resin obtained by polymerizing a regenerated monomer, they have a low gradation portion.
  • the printability was excellent, the variation in impact strength was controlled, there were no problems with general physical properties such as film elongation, wettability, and haze, and the practical performance was also excellent as shown in the bag drop test.
  • Comparative Example 1 the relative viscosity of the raw materials used was low, the mechanical properties of the obtained film were low, and the impact strength was particularly low. Due to this, cutting trouble occurred in the next process, and printing could not be performed normally.
  • Comparative Examples 2, 4 and 5 did not contain the polyamide resin obtained by polymerizing the regenerated monomer, had a large amount of terminal amino groups or carboxyl groups derived from the remelted resin, and the crystallization rate of the film raw material was increased. It is considered that as a result of the local variation in the crystallization state of the resin, the printability of the low gradation portion was lowered, and even in the bag-dropping test, the local adhesion was lowered, and the bag was easily broken. In addition, a decrease in elongation and a variation in impact strength, which are considered to be caused by impurities in the remelted resin, were also observed.
  • Comparative Example 3 the amount of monomers in the film increased as a result of sequential stretching using the same raw materials as in Comparative Example 2. As a result, the printability of the low gradation portion was locally reduced, and the result of the bag drop test was also deteriorated. There was also a decrease in elongation and variations in impact strength, which are thought to be due to impurities in the remelted resin.
  • Comparative Example 6 is a film obtained by using a polyamide resin composed of only a virgin monomer. Although there were no problems with general physical properties and practical performance, the reproducibility was inferior to that of the one using the regenerated monomer in the printability of the low gradation part.
  • Comparative Example 7 a polyamide resin composed of only virgin monomer was used, but the temperature control of the casting roll was insufficient and the surface crystallinity of the unstretched film varied, so that the unstretched film also crystallized on the surface of the film. As a result of the variation in the properties, the printability of the low gradation portion was lowered. In addition, there were some places where the accuracy of the film thickness after stretching exceeded 15%, which caused variations in impact strength and elongation.

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Abstract

Le problème décrit par la présente invention consiste à fournir un procédé de production d'un film de résine de polyamide au moyen d'une résine de polyamide obtenue par le biais d'une polymérisation d'un monomère régénéré utilisé comme un matériau recyclé. La solution selon l'invention porte sur un procédé de production d'un film de résine de polyamide qui est caractérisé en ce qu'il comprend : (1) une étape de génération d'un monomère à partir d'un matériau de dépolymérisation (A) ; (2) une étape de production d'une résine de polyamide (B) par le biais d'une polymérisation au moyen d'un matériau contenant ledit monomère ; (3) une étape de raffinage de la résine de polyamide (B) ; et (4) une étape de préparation d'un film non étiré au moyen d'un matériau de départ contenant la résine de polyamide raffinée (B), puis l'étirage du film non étiré.
PCT/JP2021/002310 2020-01-24 2021-01-22 Procédé de production de film de résine de polyamide WO2021149815A1 (fr)

Priority Applications (8)

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EP21745021.2A EP4094923A4 (fr) 2020-01-24 2021-01-22 Procédé de production de film de résine de polyamide
CN202180009922.7A CN115003735A (zh) 2020-01-24 2021-01-22 聚酰胺树脂膜的制造方法
KR1020227026856A KR102669959B1 (ko) 2020-01-24 2021-01-22 폴리아미드 수지필름의 제조방법
US17/794,030 US12012491B2 (en) 2020-01-24 2021-01-22 Method for producing polyamide resin film
JP2021572825A JP7137808B2 (ja) 2020-01-24 2021-01-22 ポリアミド樹脂フィルムの製造方法
JP2022135448A JP2022173206A (ja) 2020-01-24 2022-08-27 ポリアミド樹脂フィルムの製造方法
JP2022135449A JP2022173207A (ja) 2020-01-24 2022-08-27 ポリアミド樹脂フィルムの製造方法
US18/308,997 US20230257539A1 (en) 2020-01-24 2023-04-28 Method for producing polyamide resin film

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JP2022173207A (ja) 2022-11-18
EP4094923A1 (fr) 2022-11-30
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JPWO2021149815A1 (fr) 2021-07-29
US20230257539A1 (en) 2023-08-17
JP2022173206A (ja) 2022-11-18
TW202138440A (zh) 2021-10-16
JP7137808B2 (ja) 2022-09-15
US20230054022A1 (en) 2023-02-23
KR102669959B1 (ko) 2024-05-27
CN115003735A (zh) 2022-09-02

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